Case-hardened metals

ABSTRACT

A process of boronizing a metal article is described which comprises immersing the selected metal article in a fused bath composed of at least one alkali metal halide or alkaline earth metal halide and a boron slat of the empirical formula MxByFz wherein M is an alkali metal, and the ratio of x:y:z is 1:0.4 to 2.0:0.5 to 2.5 with y being preferably above 1 and z is preferably below 1.5, the fused bath being maintained at a temperature between 1,200* to 1,750* F. for a sufficient duration to impregnate the metal with boron. There is also described novel boron products, their process of manufacture and salt baths containing such boron products. The process produces extremely hard, uniform, adherent and corrosion resistant boride casing on metals such as carbon and alloy steels.

United States Patent [72] Inventor Oris T. Roman Las Vegas, Nev. [21] App]. No. 782,436 [22] Filed Dec. 9, 1968 [45] Patented Jan. 11, 1972 [73] Assignee Triangle Industries, Inc.

Newark, NJ.

[54] CASE-HARDENED METALS 16 Claims, No Drawings [52] U.S.Cl l48/6.11, 204/39 [51] Int. Cl C23c 9/00 [50] Field of Search 23/59; 148/6.l 1; 204/39, 60; 117/DIG. 1O

[56] References Cited UNITED STATES PATENTS 2,465,989 4/1949 Sowa 23/59 X 2,572,248 10/1951 Cooper 204/60 Primary Examiner-Ralph S. Kendall An0rneyDarby 8:. Darby ABSTRACT: A process of boronizing a metal article is described which comprises immersing the selected metal article in a fused bath composed of at least one alkali metal halide or alkaline earth metal halide and a boron slat of the empirical formula M B F wherein M is an alkali metal, and the ratio of x:y:z is 1:0.4 to 20:05 to 2.5 with y being preferably above I and z is preferably below 1.5, the fused bath being maintained at a temperature between 1,200 to 1,750 F. for a sufficient duration to impregnate the metal with boron. There is also described novel boron products, their process of manufacture and salt baths containing such boron products. The process produces extremely hard, uniform, adherent and corrosion resistant boride casing on metals such as carbon and alloy steels.

CASE-HARDENED METALS This invention relates to boron salts, their preparation and use in a fused salt bath to caseharden metals.

The inclusion of boron in carbon and low alloy steels is well known and commonly practiced in improving the hardenability of such steels. One ofthe processes used for the preparation of a boride coating on a metal comprises exposing the metal article to the vapors of a boron halide at a temperature sufficient to cause the halide to decompose and deposit a coating of boron on the metal. The metal is then heated to a still higher temperature to cause the boron to diffuse into and alloy with the metal. In the absence of a reducing gas, a displace ment reaction occurs in which some of the metal replaces the boron in the boron halide. In the presence of hydrogen, the boron halide is reduced to boron and hydrogen halide. In order to obtain satisfactory deposition rates, temperatures in the order of l,200l,400 C. are required. The deposition rate must be carefully controlled since rapid deposition results in the formation of a boride undercoating with a fused boron coating as the outermost layer. In order to obtain adherent coatings, it is usually required to deposit a very thin coating followed by a hydrogen soak to diffuse the coating into the metal. Additional coatings are made in the same manner to produce the desired thickness. This method is not satisfactory for the production of high-precision machined parts which must be accurately machined to very close tolerances before they are borided. The parts warp causing the dimensions to exceed tolerance limits because of the distortion caused by the high temperatures and phase transitions to which the article is subjected in heating and cooling, especially when repeated steps are required to produce the desired thickness of coating. The rate of deposition of the boron is very dependent on the velocity of the boron halide over the surface and the temperature of the article being coated. Since these conditions are difficult to control, especially for large or irregular shaped articles, the coatings are usually not uniform over the entire surface.

Boride coatings have also been deposited on ferrous alloys by electrolyzing a fused bath of a boron compound such as boron oxide, boric acid, borax, etc., using the ferrous alloy article as the cathode and graphite as the anode. Voltages of 4-40 volts and a current density of 50-100 amperes per square decimeter are required. Lower current densities permit the ferrous alloy to be dissolved in the bath at a rate faster than the boron is deposited on the alloy, so that there is a net weight loss. This effect is very noticeable with the boron compounds which are acidic such as boric acid or boron compounds containing boric acid as an impurity.

in more recent years boride coatings have been produced electrolytically using a fused bath composed of at least one alkali metal fluoride and at least one alkali metal fluoborate (NaBF This process is carried out in an electric cell in which an electric current is generated when an external electrical connection is made between a metal cathode and a boron anode. Preferably, additional voltage is impressed upon the circuit from an external power source. This process must be carried out in the substantial absence of oxygen, e.g., in an inert gas atmosphere or in a vacuum. Impurities have been reported to interfere with the electrode reactions and affect the quality of the boride coating. The foregoing process is costly in that it requires special equipment (e.g., an electric cell, electrodes) and carefully controlled processing conditions such as oxygen-free atmosphere, and temperatures which cannot exceed the decomposition point of the alkali metal fluoborate.

Case hardening of metals by impregnation of metal surfaces with boron has also been carried out using a boronizing bath composed of one or more borates. In such a system the boron is either introduced into the bath as elemental boron or a metal is introduced into the bath, e.g., calcium, which will in situ liberate boron from the borate base material in the bath. In the latter case the boron-liberating metal is introduced into the bath in ingot form under an inert atmosphere.

It has now been discovered that a uniform, adherent, corrosion-resistant boride coating can be produced by a simple process using a fused bath containing a boron salt of the empirical formula M,B,,F wherein M is an alkali metal, B stands for boron, and F is the fluoride ion, which does not use any ex ternally supplied electric current and is carried out under normal atmospheric conditions and temperatures at least as low as those previously employed in the prior art.

Therefore, one aspect ofthe present invention is to provide a relatively inexpensive, simple and effective diffusion process for boronizing a metal article using a fused salt bath containing a boron salt of the empirical formula M B F which does not require externally supplied electric current or special equipment or process conditions such as a boron anode, an inert atmosphere, highly purified chemicals and a specially designed electric cell.

Another aspect of the present invention relates to novel boron salts of the empirical formula M B F in which the ratio of x:y:z is 120.4 to 2:05 to 2.5 which are employed in a fused salt bath containing at least one alkali metal halide and/or alkaline-earth halide to produce a boronized metal article.

Yet another aspect of the present invention relates to boronized metal articles such as carbon and alloy steels having a uniform, adherent, tough, corrosion resistant coating and a hardness comparable to tungsten carbide.

A further aspect of the present invention relates to novel fused salt bath compositions for use in casehardening metal articles.

An additional aspect of the invention relates to processes of producing the novel boron salts of the empirical formula M,B,,F, wherein the ratio ofx:y:z is 1:0.4 to 2:05 to 2.5.

These and other aspects of the present invention will become apparent from the following description:

Unexpectedly, it has now been discovered that a uniform, nonporous, adherent, corrosion-resistant coating can be formed on specific metals by a diffusion process employing a fused salt bath wherein an electrical circuit is formed through an electrical connection, which is external to the salt bath, between the pot containing the salt bath and the metal sample holder which holds the sample to be borided. This process produces boronized metal articles of extremely high hardness which is at least equal to and in many cases substantially greater than the hardness heretofore attainable in borided metals obtained in accordance with prior art processes.

As used herein a boride case means any solid solution or alloy of boron and metal regardless of whether the metal forms an intermetallic compound with boron (e.g., FeB or Fe B in a boronized ferrous base alloy) in stoichiometric proportions which can be represented by a chemical formula. The expression boronized metal means a metal article in which boron has been diffused into the core of the metal without forming a substantial overlying boron coating on the surface of the metal article.

The boronizing process of my invention may be carried out in a stainless steel or silicon carbide pot. An electric circuit is formed external to the fused salt bath by using a conductor to join the pot containing the salt bath to the metal holder from which the sample is suspended into the bath. The salt bath contains at least one alkali metal halide and/or alkaline earth halide in addition to the selected novel boron salt, The boron products produced by the present invention have not been definitely proven to be chemical compounds as contrasted with mixtures and therefore will be referred to as chemical products. The novel boron products of this invention conform to the empirical formula M B F in which M is an alkali metal. e.g., sodium, lithium, potassium, etc., B is boron, F is a fluoride ion and the ratio of x.'y:z is 110.4 to 2:05 to 2.5. The preferred products used in the fused salt bath have the empirical formula M B F wherein M is an alkali metal and the ratio ofx:y:z is l:l to 2:0.5 to 1.5.

These novel boron salts may be produced by reducing an alkali metal fluoborate with a reducing agent such as amorphous boron. Other reducing agents such as oxalic acid, sodium borohydride, metallic alkali metals, e.g., sodium. potassium, etc.. mixtures of amorphous boron with metallic sodium, etc., can be employed suitably for reducing the alkali metal fluoborate. The foregoing process is carried outjust above the melting point ofthe alkali metal fluoborate that is being used.

While the alkali metal boron salts of the empirical formula M B F are the more desirable boron salts, it is also possible to use the corresponding alkaline earth salts in a fused salt bath to boronize a metal. The drawback to using alkaline earth boron salts in place of alkali metal boron salts, particularly when treating ferrous alloys is that the alkaline earth boron salts have substantially higher melting and decomposition points than the corresponding alkali metals. Hence, in boronizing steel the required operating temperatures would damage the ferrous alloy causing warpage, distortion, etc., which is obviously undesirable. However, in boronizing metals such as tungsten, molybdenum and other metals which will not be damaged at the high temperature required for melting the alkaline earth boron salts in the fused bath such salts can be employed to good advantage.

The aforedescribed boron salts are employed in accordance with the invention in a fused salt bath composed of the selected boron salt and at least one alkali metal halide and/or alkaline earth halide. Since it is desirable to use as low a tern perature as practical to avoid damaging or distorting the metal article to be borided, a mixture of at least two alkali metal halides is preferred to provide a salt bath having lower fusion temperatures than the individual components. As used herein alkali metals and alkaline earth metals mean those metals set forth in the Periodic Chart of elements which fall within these two classifications.

It has been found that a good, adherent and tough borided metal article is obtained ifthe salt bath contains from about IO to 40 percent by weight of the selected boron salt M B F preferably from 20 to 35 percent by weight. The predominant portion ofthe bath is made up of alkali metal and/or alkaline earth metal halides. The selected boron salt comprises about to about 35 percent by weight of the alkali metal halide and/or alkaline earth halide salts present in the bath. Preferably, alkali metal halides are used in the bath because they provide salt baths with lower fusion temperatures. As previously indicated, at least two alkali metal halide salts are preferably used, with one of these salts comprising preferably at least about 50 percent by weight of the salt bath. However, satisfactory results may also be obtained where no one alkali metal halide salt comprises at least 50 percent by weight ofthe bath composition.

The selection of the particular combination of alkali metal halide salts for use in the salt bath is not critical. However, it has been found that optimum results are obtained when the cation portion of the predominant alkali metal halide or alkaline earth halide salt in the bath is the same as the cation portion of the boron salt in the bath. Results are further optimized if the cation portion of one of the alkali metal halides in the bath is of the next lower period, in the Periodic Table than the other alkali metal halide. Thus, ifthe one alkali metal halide is KCl, the other alkali metal halide is preferably NaCl.

The anion portion ofthe boron salt in the fused bath may be the same as or different from the anion portion of the alkali metal halide salts in the bath. Best results are obtained if the anion portion of the alkali metal or alkaline earth metal salts are chlorides, because this reduces the corrosive effects ofthe salt bath.

The operating temperature of the fused salt bath is determined by numerous factors including the nature and charac' teristics of the metal to be borided and the melting temperature of the bath. in general, a bath formed in accordance with the present invention is useful for boronizing at any temperature between its melting point and its boiling point provided that the selected metal to be boronized or the case obtained, is not damaged at the selected temperature. In order to produce a reasonably fast boronizing rate and achieve adequate penetration of the boron into the selected metal immersed in the fused salt bath, it is desirable to maintain the salt bath at a temperature no lower than about l,250 F. While lower temperatures may be used, it has been found that the degree of penetration of the boride case and the thickness of the case are adversely affected because the fluidity of the bath is substantially reduced. Best results are obtained when the fused salt bath is highly fluid. For carbon and alloy steels the bath temperature is maintained between 1,250" and l.700 F. during the boronizing process, the higher end of the temperature range being used for stabilized steels and the lower end of the temperature range for mild steels.

Temperatures should be avoided which will result in annealing of the product and which will damage or distort the metal article to be borided. With other metals to be case hardened such as tungsten, tantalum, niobium, molybdenum, etc., bath temperatures up to 2,000 F. could be used.

It has been found that the thickness of the boride case and the degree of penetration is a function of immersion time in the bath, temperature of the salt bath, boron content of the bath, and the properties of the metal article to be treated. A good boride case has been obtained after about 2-hours' immersion ofa low carbon steel in the fused salt bath. Obviously the rate of boron diffusion is not the same for every metal. Hence, the treatment conditions necessary to obtain the desired case thickness and penetration may vary from one metal to another. With regard to ferrous alloys it has been found that the degree of penetration is higher in low-carbon steels than in high-alloy steels. The preferred time of immersion in the boronizing bath is variable and depends upon a number of factors including the thickness of the case desired, the bath temperature and the characteristics of the metal article being boronized.

The current density generated by the external electrical connection between the pot and the specimen holder from which the specimen is immersed in the salt bath varies with the temperature of the bath, the specimen size and the percent boron in the product of the empirical formula M B F, Usually the current density lies between about 50 microamperes at 1,200 F. and 300 microamperes at about l,600 F. using a rod 3 inches long and having a diameter of0.5 inch.

The process of this invention has produced boride cases having a thickness of at least 2 mils and thicknesses over 15 mils have been obtained. it has been observed that the original dimensions of the treated metal article does not change substantially.

The boronizing process of my invention is applicable to a large number of metals. Excellent casehardened products have been obtained with ferrous alloys such as low-carbon steels and highalloy steels. With steels having a high-carbon content, such as in 1080 steel, the penetration is somewhat less due to the higher carbon content. Other metals which may be borided by my process are those into which boron will diffuse such as metals having atomic numbers 22-28 inclusive, 41-46 inclusive, and 73-78 inclusive. This range of atomic numbers includes those metals included in the periodic chart of the elements shown on pages 56 and 57 of Lange's Handbook of Chemistry, 9th edition, Handbook Publishers, lnc., Sandusky, Ohio, [956, such as the group VB metals, which are vanadium, niobium and tantalum, group VlB metals, which are chromium, molybdenum and tungsten, group VllB metals such as manganese and group Vlll metals such as iron, cobalt and nickel. Alloys of these metals with each other, or alloys containing these metals as the major constituent, i.e., over 50 mole percent but usually over 75 mole percent and preferably at least mole percent, alloyed with other metals as a minor constituent, i.e., less than 50 mole percent but usually less than 25 mole percent and preferably less than 10 mole percent, can also be borided by my process, providing the melting point of the resulting alloy is not less than l,700 F. The fact that other metals may be the minor constituents of an alloy with the metals with which this invention is concerned does not prevent the formation of the desired boride case. These minor constituents may be any of the other metals of the periodic system, i.e., the metals of groups lA, A, B, lllA, lllB, IVA, lVB, VA and WA. These metals have atomic numbers 34 inclusive, 1 l-13 inclusive, l9-2l inclusive. 3033 inclusive, 37-40 inclusive, 485l inclusive, 55-72 inclusive, 80-84 inclusive and 8798 inclusive.

After the boronized metal is removed from the salt bath it is cooled. The selected method of cooling is not critical However, care should be exercised to select a method of cooling that does not adversely affect previously established characteristics of the boronized metal. Air cooling or using a quenching oil have been found most satisfactory, but other cooling cycles may be used as necessary to obtain the desired substrate qualities. After the boronized sample is cooled it is further treated by conventional techniques to remove residual salts that may be adhering to the metal surface.

The following examples are given by way of illustration and not by way of limitation. It is readily apparent that variations from the specific reaction conditions and reactants may be made without departing from the scope of the invention.

EXAMPLE 1 To 330 grams of sodium fluoborate placed in a steel crucible there was added 22 grams of amorphous boron, the mixture was heated just above the melting point of the sodium fluoborate which is 384 C. for approximately 2 hours. The crucible and its contents were cooled and the recovered product was found to weigh 248 grams. The product removed was a cakelike solid mass which was pulverized into a powderlike material.

A suitable sample of the solid material was analyzed by analytical chemical techniques and identified as having the empirical formula Na,B,,F wherein the ratio of xcyzz is l:l.22:l.33.

EXAMPLE 2 To 330 grams sodium fluoborate placed in a steel crucible there was added I 1 grams amorphous boron, the mixture was heated just above the melting point of the sodium fluoborate (i.e., 384 C.) for approximately 2 hours. The recovered product was found to weigh 262 grams and upon analysis was indicated to have the empirical formula Na,B,,F wherein the ratio ofx:y:z is l:O.83:l.l.

EXAMPLE 3 The process of example 1 was repeated except that 44 grams of amorphous boron was used. The resulting product had the empirical formula Na,B,,F wherein the ratio of x:y:z is l:l.7:0.95.

EXAMPLE 4 To 330 grams sodium fluoborate in a steel crucible were added 46 grams metallic sodium beads and 22 grams of amorphous boron. The mixture was heated for 2 hours at a temperature above the melting point of sodium fluoborate, after which the crucible was cooled and the material removed. Upon analysis this material had the empirical formula Na,B,,F z wherein the ratio ofx:y:z is 1:08: I .8.

EXAMPLE 5 To 378 grams potassium fluoborate was added 22 grams amorphous boron, the materials being well mixed. The mixture was heated to a temperature above 530 C., the melting point of potassium fluoborate, for approximately 2 hours. The recovered product was found to weight 312 grams. This product was analyzed chemically and found to have the empirical formula K,B,,F wherein the ratio of x:y:z is 121. 1622.42.

EXAMPLE 6 To 281 grams lithium fluoborate was added 43.6 grams amorphous boron, these materials being well mixed. The mixture was heated to a temperature above 300 C. for approximately 2 hours. The crucible and its contents were cooled and the recovered product found to weigh l70 grams. This product was analyzed chemically and found to have the empirical formula Li,B,,F wherein the ratio of xzyzz is l:l.9:0.5.

EXAMPLE 7 A product having the empirical formula Na B F in which the ratio of x:y:z is 1:0.4:l.3 was produced by heating l mole sodium fluoborate with 1 mole of oxalic acid, in a steel crucible just above the melting point of the oxalic acid (i.e., 101 C.) for 6 hours driving off carbon dioxide, water and hydrofluoric acid.

EXAMPLE 8 A product having the empirical formula Na,B,,F in which the ratio of xzyzz is about 1:0.9: 1 .2 was produced as described in example 4 by mixing 330 grams sodium fluoborate, ll5 grams metallic sodium and 66 grams amorphous boron.

EXAMPLE 9 Into a steel vessel there was placed 1,000 grams sodium chloride, 500 grams lithium chloride and 400 grams of the product of the empirical formula Na ,B,,F, produced in example 1. These materials were heated to a temperature of about l,400 F. to produce a clear fluid fused salt bath. In this bath there was suspended from stainless steel wire a rod (0.5 inches diameter 3 inches long) of 1018 steel having a carbon content of 0.17 percent. The metal wire holder from which the rod is suspended was joined by a conductor to the pot handle thereby forming an electric circuit external to the fused salt bath. This circuit operates as a self-generating cell. The rod remained immersed in the bath for about 6 hours, and was then removed from the bath and permitted to air cool.

The sample had a hard, uniform, smooth, adherent boride layer which proved to be 3-mil thick upon photomicrograph examination. The microhardness was measured in accordance with the Knoop hardness test using a IOO-gram load and found to be about 2,000. This boride case is as hard as tungsten carbide and much harder than typical 'nitrided or carburized cases (300 to 1,000 Knoop value). Dimensional analysis showed that after immersion in the bath the original thickness ofthe rod changed less than 1 mil.

Some of the boride case was removed and examined by X- ray diffraction analysis. Substantial amounts of Fe B and FeB were detected.

The boron content ofthe case of this example was about 3.5 percent by weight of total surface material as determined by chemical analysis.

EXAMPLE l0 Into a stainless steel vessel there was placed 750 grams sodium chloride, 750 grams lithium chloride and 400 grams of the product of the empirical formula Na,B,,F produced in example 8. These materials were heated to a temperature of about 1,600" F. In this bath there was immersed a rod (0.5 inches diameter 3 inches long) of 1018 steel having a carbon content of 0.17 percent. An external electrical connection was made as previously described. The rod remained in the bath for 8 hours and was removed and oil quenched.

The sample had a hard, uniform, smooth adherent boride layer which proved to be 6-mils thick upon photomicrograph examination. The microhardness was measured in accordance with the Knoop hardness test using a lOO-gram load and found to be about 2,200. Dimensional analysis showed that after immersion in the bath the original thickness of the rod changed less than 2 mils.

EXAMPLE ll Into a stainless steel vessel there was placed 720 grams of calcium chloride, 465 grams of barium chloride, and 400 grams of the product having the empirical formula Na B F produced in example 1. The bath was heated to about 1,600 F. at which point it was molten but carried a soft opaque crust of insoluble constituents. In this bath was immersed a rod V2- inch diameter and 3 inches long of 1018 steel. An external electrical connection was made as previously described. The rod was allowed to remain immersed for about 6 hours, was then removed from the bath and oil quenched. The specimen had a hard borided layer which proved to be over 3-mils thick upon photomicrograph examination and the Knoop value was found to be about 2,100 using a 100-gram gram load. The case was not as uniform as that obtained in example 9 or example 10.

Samples of 1018 steel immersed for longer periods of time, and for various periods of time at higher temperatures, up to 1,700 F. in the same bath, exhibited deeper cases but no improvement in uniformity.

EXAMPLE l2 1n the salt bath described above in example 10, there was placed a hexagon-shaped steel machine nut having a /2-inch nominal inside diameter and 13 threads per inch. The nut was fabricated ofa low-carbon steel, with a grain structure similar to that of 1018 or 1020 steel. The nut was oriented in the salt bath so that the polar axis of the threads was vertical, permitting natural convection of the hot salts to induce vertical salt flow upwards through the nut. This run was carried out at 1,600 F. for 8 hours. The nut was then removed from the salt bath, air cooled, split, mounted and examined metallographically. A hard, uniform hard borided case had been formed on the surface of the nut, including the roots, faces and crowns of the threads. Variations in the case thickness between the thread crowns and thread roots was less than 10 percent, a substantial improvement over electroplating of similar surfaces. The thickness of the case was measured to be 3.5 mils average and the hardness varied from 2,270 to 2,470 Knoop, taken with a IOO-gram load.

EXAMPLE 13 in the salt bath described above in example 9, heated to l,500 F., there was placed a /z-inch by 3-inch long bar of 1137 steel. After 8 hours treatment in the salt bath, the specimen was removed, air cooled, sectioned and examined metallographically. A hard, smooth uniform borided case was formed on the surface of the specimen, averaging 4 mils thick and having a hardness ofover 1,900 Knoop, taken with a 100- gram load.

EXAMPLE 14 in the salt bath described above in example 9 there were placed 6 rods of4140 steel, each having a diameter of /2-inch and length of 3 inches. The salt bath was maintained at 1,600 F. throughout the length of the experiment. The 6 rods were singly withdrawn from the salt bath and allowed to air cool at 2-hour intervals; e.g., the first was withdrawn after 2 hours in the salt bath, the second after 4 hours, etc., and the sixth after 12 hours immersion in the bath. Each sample was then sectioned and examined metallographically. A hard smooth uniform borided case had formed on each rod, of nearly equal hardness but with thickness of case varying according to the following table:

The hardness of the cases on these samples varied from 1,900 t0 2,100 Knoop, taken with a lOO-gram load.

EXAMPLE 15 Into the salt bath described above in example 9, there was placed a rod of 1045 steel, having a diameter of /2-inch and length of 3 inches. The salt bath was maintained at a temperature of 1,400 F. for 8 hours, after which the 1045 rod was removed and air cooled. The bath was then heated to 1,500 F. and a second rod ofequal size and shape of 1045 steel was immersed in the salt bath for 8 hours, removed and air cooled. This was repeated, using /-inch by 3-inch rods of 1045 steel for 8-hour treatments, at 1,550 F., 1,600 F., 1,650 F. and 1,700 F. All rods were then sectioned and examined metallographically. Each had a hard, smooth, uniform borided case of nearly equal hardness-1,900 to 2,100 Knoop, as taken with a IOO-gram load. The thickness of the cases on the rods varied according to the following table:

Temperature F. Case '1 hickncss (mils) EXAMPLE 16 into the bath described above in example 9, there was placed a 0.040-inch diameter molybdenum wire 6 inches long. The salt bath was held at 1,700 F. for 12 hours. The wire was then withdrawn from the bath, air cooled, sectioned into several Ari-inch lengths and examined metallographically. A very hard case had formed on the wire and was diffused 2 mils into the wire substrate. This case was 3-mils thick, had a hardness of2,940 Knoop, taken with a -gram load.

EXAMPLE l7 Into the bath described above in example 10, there was placed a 41-inch diameter tungsten rod. The salt bath was held at 1,700 F. for 4 hours. The rod was then withdrawn from the bath, air cooled, sectioned into several lengths and examined metallographically. A very hard case had formed on the rod which was l.5-mi1s thick and had a hardness value of 4,200 Knoop, taken with a IOO-gram load.

EXAMPLE 18 in the bath described in example 10 there was placed l/32- inch thick tantalum sheet. The salt bath was held at 1,700 F. for 1 hour. The sheet was removed from the bath and treated as described in the previous example. A boron case was obtained having a thickness of 0.5 mils and a knoop hardness value of about 4,200 using a lOO-gram load.

A 1/16-inch thick titanium sheet was processed in the same bath at 1,600 F. for 12 hours. A boron case was obtained having a thickness of 1 mil and a Knoop hardness value above 4,200 using a l00-gram load.

The metals borided in accordance with the present invention have numerous uses particularly where a high hardness, uniform, adherent tough, corrosion resistant product is desired. Thus, it is useful for improving the hardenability of ferrous alloys and providing good electrical conductors with tungsten, molybdenum and tantalum. Hence, for example, the borided products produced in accordance with the present process can be fabricated into parts for aircraft engines, spacecraft, farm equipment, etc. Other uses will be readily apparent to those skilled in the art.

The above examples are illustrative of the preferred embodiments of the invention. However, other modifications can be made without departing from the scope of the present invention. It is therefore to be understood that changes may be made in the embodiment of the invention which are within the full intended scope of the invention as defined by the appended claims.

What is claimed is l. A product of the empirical formula M B F wherein M is an alkali metal, B is boron, F is the fluoride ion and the ratio of xzyzz is l:0.4 to 2:0.5 to 2.5.

2. A product according to claim 1 wherein the ratio of x:y:z is 1:1 to 2:0.5 to L5.

3. A product according to claim 1 wherein the alkali metal is sodium.

4. A fused salt bath composition comprising (a) a product of the empirical formula M B F wherein M is an alkali metal, B is boron, F is the fluoride ion and in which the ratio of xzyzz is 1:0.4 to 2:0.5 to 2.5 and (b) at least one halide salt selected from the class consisting of alkali metal halides and alkali earth halides, said halide salt being the predominant salt in said bath and said product defined in (a) comprising about to about 35 percent by weight of said halide salt in said bath.

5. A salt bath according to claim 4 wherein said halide salt comprises two different alkali metal halides.

6. A salt bath according to claim 5 wherein the ratio of xzyzz is 1:1 to 2:0.5 to 1.5.

7. A salt bath according to claim 5 wherein said alkali metal halides are alkali metal chlorides.

8. A salt bath according to claim 5 wherein the cation portion ofone of said alkali metal halides is the same as the cation portion of said product of the empirical formula M,B,,F,.

9. A salt bath according to claim 8 wherein said cation portion is sodium.

10. A salt bath according to claim 4 wherein said product defined in (a) comprises about 20 to 35 percent by weight of said salt bath composition.

11. A salt bath according to claim 10 wherein said alkali metal chlorides are sodium chloride and lithium chloride.

12. A salt bath according to claim 10 wherein said alkali metal chlorides are potassium chloride and sodium chloride.

13. A salt bath according to claim 10 wherein said alkali metal halides comprise at least 50 percent by weight of said salt bath composition.

14. A fused salt bath composition comprising (a) a product of the empirical formula M,B,,F, wherein M is an alkali metal, B is boron, F is the fluoride ion and the ratio of xzyzz is 120.4 to 2:0.5 to 2.5 and (b) at least two alkali metal chlorides, said product of the empirical formula M,B,,F comprising about 20 to about 35 percent by weight of said salt bath composition.

15. A fused salt bath according to claim 14 wherein said alkali metal chlorides are sodium chloride and lithium chloride.

16. A fused salt bath according to claim 15 wherein M is sodium. 

2. A product according to claim 1 wherein the ratio of x:y:z is 1:1 to 2:0.5 to 1.5.
 3. A product according to claim 1 wherein the alkali metal is sodium.
 4. A fused salt bath composition comprising (a) a product of the empirical formula MxByFz wherein M is an alkali metal, B is boron, F is the fluoride ion and in which the ratio of x:y:z is 1:0.4 to 2:0.5 to 2.5 and (b) at least one halide salt selected from the class consisting of alkali metal halides and alkali earth halides, said halide salt being the predominant salt in said bath and said product defined in (a) comprising about 10 to about 35 percent by weight of said halide salt in said bath.
 5. A salt bath according to claim 4 wherein said halide salt comprises two different alkali metal halides.
 6. A salt bath according to claim 5 wherein the ratio of x:y:z is 1:1 to 2:0.5 to 1.5.
 7. A salt bath according to claim 5 wherein saiD alkali metal halides are alkali metal chlorides.
 8. A salt bath according to claim 5 wherein the cation portion of one of said alkali metal halides is the same as the cation portion of said product of the empirical formula MxByFz.
 9. A salt bath according to claim 8 wherein said cation portion is sodium.
 10. A salt bath according to claim 4 wherein said product defined in (a) comprises about 20 to 35 percent by weight of said salt bath composition.
 11. A salt bath according to claim 10 wherein said alkali metal chlorides are sodium chloride and lithium chloride.
 12. A salt bath according to claim 10 wherein said alkali metal chlorides are potassium chloride and sodium chloride.
 13. A salt bath according to claim 10 wherein said alkali metal halides comprise at least 50 percent by weight of said salt bath composition.
 14. A fused salt bath composition comprising (a) a product of the empirical formula MxByFz wherein M is an alkali metal, B is boron, F is the fluoride ion and the ratio of x:y:z is 1:0.4 to 2:0.5 to 2.5 and (b) at least two alkali metal chlorides, said product of the empirical formula MxByFz comprising about 20 to about 35 percent by weight of said salt bath composition.
 15. A fused salt bath according to claim 14 wherein said alkali metal chlorides are sodium chloride and lithium chloride.
 16. A fused salt bath according to claim 15 wherein M is sodium. 